TW202428806A - Polishing compositions and methods of use thereof - Google Patents

Abstract

This disclosure relates to a polishing composition that includes an abrasive, at least two pH adjusters, a barrier film removal rate enhancer, a low-k removal rate inhibitor; and an azole-containing corrosion inhibitor. This disclosure also features a method of using the polishing composition to polish a substrate containing copper and silicon oxide.

Description

Polishing composition and method of use thereof

Related applications

This application claims priority to U.S. Provisional Application No. 63/428,550 filed on November 29, 2022, the contents of which are hereby incorporated by reference in their entirety.

The present invention relates to polishing compositions and methods of using the same.

Invention Background

Process and integration innovations continue to drive the semiconductor industry to improve chip performance through further device miniaturization. Chemical Mechanical Polishing/Planarization (CMP) is a powerful technology because it enables many complex integration schemes at the transistor level, thereby promoting chip density increases.

CMP is a process used to flatten/planarize a wafer surface by removing material using both a wear-based physical process and a surface-based chemical reaction. In general, a CMP process involves applying a CMP slurry (aqueous chemical formulation) to the wafer surface while contacting the wafer surface with a polishing pad and moving the polishing pad relative to the wafer. The slurry typically includes an abrasive component and dissolved chemical components, which can vary significantly depending on the materials present on the wafer that will interact with the slurry and polishing pad during the CMP process (e.g., metals, metal oxides, metal nitrides, dielectric materials such as silicon oxide, silicon nitride, etc.).

Many currently available CMP slurries are specifically designed to remove materials that are more common in older chip designs. However, chip designs and architectures are constantly changing, and certain components in these older CMP slurries may result in detrimental and/or unacceptable defect counts.

Summary of the invention

This summary is provided to introduce a selection of concepts that are further described below in the embodiments. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to help limit the scope of the claimed subject matter.

As defined herein, all percentages expressed are to be understood as weight percentages relative to the total weight of the chemical mechanical polishing composition, unless otherwise indicated.

In one aspect, embodiments disclosed herein relate to a polishing composition comprising an abrasive, at least two pH adjusters comprising at least one inorganic base and at least one organic base, wherein the molar ratio of the at least one organic base to the at least one inorganic base is from about 0.05 to about 2; a barrier film removal rate enhancer; a low-k removal rate suppressor; and an azole-containing corrosion suppressor.

In yet another aspect, embodiments disclosed herein relate to a method of polishing a substrate, comprising the steps of applying a polishing composition described herein to a surface of a substrate, wherein the surface comprises copper and silicon oxide; and contacting a pad with the surface of the substrate and moving the pad relative to the substrate.

Other aspects and advantages of the claimed subject matter will become apparent from the following description and appended claims.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Embodiments disclosed herein generally relate to compositions and methods of using the compositions to polish substrates that include at least a copper portion and more particularly include at least silicon oxide and copper portions. In some embodiments, it is desirable to remove silicon oxide and copper at similar removal rates. The inventors have unexpectedly discovered that the compositions disclosed herein can effectively suppress oxide dishing and edge erosion, minimize copper line height differences between thin and wide lines, and reduce abrasive-related particle residues on the wafer surface after polishing, while still effectively maintaining similar removal rates between copper and silicon oxide. For example, the compositions disclosed herein may be particularly useful for polishing advanced node films including copper, ruthenium liners, barriers (eg, Ta, TaN), and dielectric materials (eg, TEOS, low-k, ultra-low-k, etc.).

In one or more embodiments, the polishing composition described herein includes an abrasive; at least two pH adjusters, wherein at least one pH adjuster is an inorganic base and at least one pH adjuster is an organic base; a barrier film removal rate enhancer; a low-k removal rate suppressor; and an azole-containing corrosion inhibitor. In one or more embodiments, a polishing composition according to the present disclosure may include about 0.1 wt % to about 50 wt % of an abrasive, about 0.05 wt % to about 10 wt % of a total pH adjuster (i.e., including both an inorganic base and an organic base), about 0.02 wt % to about 4 wt % of a barrier film removal rate enhancer, about 0.005 wt % to about 5 wt % of a low-k removal rate inhibitor, about 0.0001 wt % to about 1 wt % of an azole-containing corrosion inhibitor, and the remaining weight percent (e.g., about 20 wt % to about 99 wt %) of a solvent (e.g., deionized water).

In one or more embodiments, the present disclosure provides a concentrated polishing composition that can be diluted up to two times, or up to four times, or up to six times, or up to eight times, or up to ten times with water prior to use. In other embodiments, the present disclosure provides a point-of-use (POU) polishing composition comprising the above polishing composition, water, and optionally an oxidizing agent for use on a substrate (e.g., a substrate containing copper and silicon oxide).

In one or more embodiments, the POU polishing composition may include about 0.1 wt % to about 12 wt % of an abrasive, about 0.05 wt % to about 5 wt % of a total pH adjuster (i.e., including both an inorganic base and an organic base), about 0.02 wt % to about 2 wt % of a barrier film removal rate enhancer, about 0.005 wt % to about 0.5 wt % of a low-k removal rate inhibitor, about 0.0001 wt % to about 0.1 wt % of an azole-containing corrosion inhibitor, optionally about 0.1 wt % to about 5 wt % of an oxidizing agent, and about 80 wt % to about 99 wt % of a solvent (e.g., deionized water). In one or more embodiments, the POU polishing composition can further include about 0.001 wt % to about 0.1 wt % of a chelating agent.

In one or more embodiments, the concentrated polishing composition may include about 1 wt % to about 50 wt % of an abrasive, about 0.5 wt % to about 10 wt % of a total pH adjuster (i.e., including both inorganic and organic bases), about 0.2 wt % to about 4 wt % of a barrier film removal rate enhancer, about 0.05 wt % to about 5 wt % of a low-k removal rate inhibitor, about 0.001 wt % to about 1 wt % of an azole-containing corrosion inhibitor, and the remaining weight percentage (e.g., about 20 wt % to about 98.5 wt %) of a solvent (e.g., deionized water). In one or more embodiments, the concentrated polishing composition may further include about 0.01 wt % to about 1 wt % of a chelating agent.

In one or more embodiments, the polishing composition described herein may include at least one (e.g., two or three) abrasives. In some embodiments, the at least one abrasive is selected from the group consisting of a cationic abrasive, a substantially neutral abrasive, and a cationic abrasive. In one or more embodiments, the at least one abrasive is selected from the group consisting of aluminum oxide, silicon dioxide, titanium oxide, barium oxide, zirconium oxide, co-formed products thereof (i.e., co-formed products of aluminum oxide, silicon dioxide, titanium oxide, barium oxide, or zirconium oxide), coated abrasives, surface modified abrasives, and mixtures thereof. In some embodiments, the at least one abrasive does not include barium oxide. In some embodiments, at least one abrasive is of high purity and may have less than about 100 ppm of alcohol, less than about 100 ppm of ammonia, and less than about 100 ppb (parts per billion) of alkaline cations, such as sodium cations. The abrasive may be present in an amount of about 0.1% to about 12% (e.g., about 0.5% to about 10%) or any subrange thereof, based on the total weight of the POU polishing composition.

In some embodiments, the amount of at least one abrasive is at least about 0.1% by weight (e.g., at least about 0.5%, at least about 1%, at least about 2%, at least about 4%, at least about 5%, at least about 10%, at least about 12%, at least about 15%, or at least about 20%) to at most about 50% by weight (e.g., at most about 45%, at most about 40%, at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 12%, at most about 10%, or at most about 5%) of the polishing composition described herein.

In one or more embodiments, the average particle size of at least one abrasive can be at least about 1 nm (e.g., at least about 5 nm, at least about 10 nm, at least about 20 nm, at least about 40 nm, at least about 50 nm, at least about 60 nm, at least about 80 nm, or at least about 100 nm) to at most about 1000 nm (e.g., at most about 800 nm, at most about 600 nm, at most about 500 nm, at most about 400 nm, at most about 200 nm, at most about 150 nm, or at most about 100 nm). As used herein, mean particle size (MPS) is determined by dynamic light scattering techniques.

In one or more embodiments, the polishing composition described herein may include at least two (e.g., three or four) pH adjusters. In one or more embodiments, the polishing composition described herein may include a single pH adjuster, which is an inorganic base or an organic base. In one or more embodiments, the pH adjuster includes at least one (e.g., two) inorganic bases and at least one (e.g., two) organic bases. In some embodiments, the inorganic base may be selected from the group consisting of ammonium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, arsenic hydroxide, and any combination thereof.

In one or more embodiments, the pH adjuster includes a first organic base and optionally a second organic base different from the first organic base. In some embodiments, the first organic base is a quaternary ammonium hydroxide (e.g., an alkylammonium hydroxide, such as a tetraalkylammonium hydroxide), a quaternary phosphonium hydroxide (e.g., an alkylphosphonium hydroxide, such as a tetraalkylphosphonium hydroxide), or a guanidine compound (e.g., guanidine or a compound including a guanidine group). In one or more embodiments, the quaternary ammonium hydroxide is selected from the group consisting of tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, diethyldimethylammonium hydroxide, dimethyldipropylammonium hydroxide, benzyltrimethylammonium hydroxide, and any combination thereof. In one or more embodiments, the quaternary phosphonium hydroxide is selected from the group consisting of tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrapropylphosphonium hydroxide, tetrabutylphosphonium hydroxide, tetrapentylphosphonium hydroxide, triethyl-methyl-phosphonium hydroxide, tetrakis(hydroxymethyl)phosphonium hydroxide, tetraphenylphosphonium hydroxide, and any combination thereof. In one or more embodiments, the first organic base (i.e., quaternary ammonium hydroxide or quaternary phosphonium hydroxide) does not include a covalently bonded hydroxyl group (e.g., does not include choline hydroxide or tris(2-hydroxyethyl)methylammonium hydroxide). In one or more embodiments, the guanidine compound is selected from the group consisting of guanidine, metformin, phenformin, buformin, proguanil, morpholineguanidine, 1,3-diphenylguanidine, 1,1,3,3-tetramethylguanidine, 1,2,3-triphenylguanidine, 1-(tert-butyloxycarbonyl)guanidine, inositol phosphate, N-tosyl-L-arginine, 1,3-di-o-tolylguanidine, and any combination thereof.

In one or more embodiments, the optional second organic base does not include quaternary ammonium hydroxide or quaternary phosphonium hydroxide. In one or more embodiments, the optional second organic base is selected from the group consisting of alkylamines, amino alcohols, guanidines, cyclic amines, and mixtures thereof. In one or more embodiments, the optional second organic base is selected from the group consisting of monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, (triethyl)amine, monopropylamine, dipropylamine, tri-n-propylamine, monobutylamine, dibutylamine, tributylamine, 2-aminopropane (isopropylamine), ethanolamine, diethanolamine, triethanolamine, 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-dimethylamino-2-methylpropanol, tris(hydroxymethyl)aminomethane, 2-amino-2-ethyl-1,3-propanediol, 3-amino-4-octanol, aminopropyldiethanolamine, 2-[(3-aminopropyl)methylamino]ethyl alcohol, 2-(2-aminoethoxy)ethanol, 2-(3-aminopropylamino)ethanol, 2-dimethylaminoethanol, cysteamine, guanidine, metformin, phenformin, buformin, proguanil, morpholineguanidine, 1,3-diphenylguanidine, 1,1,3,3-tetramethylguanidine, 1,2,3-triphenylguanidine, 1-(tert-butyloxycarbonyl)guanidine, inositol phosphate, N-tosyl-L-arginine, 1,3-di-o-tolylguanidine, 1,8-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene, and mixtures thereof.

In one or more embodiments, the combined amount of the pH adjuster (e.g., at least one inorganic base and at least one organic base (e.g., including the optional second organic base, if present)) is at least about 0.05 wt % (e.g., at least about 0.1 wt %, at least about 0.2 wt %, at least about 0.4 wt %, at least about 0.5 wt %, at least about 0.8 wt %, at least about 1 wt %, at least about 2 wt %, at least about 5 wt %, or at least about 7 wt %) to at most about 10 wt % (e.g., at most about 9 wt %, at most about 8 wt %, at most about 7 wt %, at most about 6 wt %, at most about 5 wt %, at most about 4 wt %, at most about 3 wt %, at most about 2 wt %, at most about 1 wt %, at most about 0.5 wt %, at most about 0.2 wt %, or at most about 0.1 wt %) of the polishing composition described herein. In one or more embodiments, the molar ratio of the total amount of the organic base (e.g., the first organic base and the optional second organic base) to the total amount of the inorganic base (e.g., organic base:inorganic base) can be at least about 0.05 (e.g., at least about 0.1, at least about 0.2, at least about 0.3, at least about 0.4, at least about 0.5, at least about 0.6, at least about 0.7, at least about 0.8, at least about 0.9, at least about 1, at least about 1.1, at least about 1.2, or at least about 1.3) to at most about 2. (e.g., a value of at most about 1.9, at most about 1.8, at most about 1.7, at most about 1.6, at most about 1.5, at most about 1.4, at most about 1.3, at most about 1.2, at most about 1.1, at most about 1, at most about 0.9, at most about 0.8, at most about 0.7, at most about 0.6, or at most about 0.5).

In one or more embodiments, the pH of the polishing composition can be at least about 7 (e.g., at least about 7.5, at least about 8, at least about 8.5, at least about 9, at least about 9.5, at least about 10, at least about 10.5, at least about 11, at least about 11.5, or at least about 12) to at most about 14 (e.g., at most about 13.5, at most about 13, at most about 12.5, at most about 12, at most about 11.5, at most about 11, at most about 10.5, at most about 10, at most about 9.5, or at most about 9). Without wishing to be bound by theory, it is believed that polishing compositions having a pH below 7 will significantly increase corrosion and particle retention, and polishing compositions having a pH above 14 may affect the stability of the suspended abrasive and will significantly increase roughness and reduce the overall quality of films polished by such compositions. To obtain the desired pH, the relative concentrations of the ingredients in the polishing compositions described herein may be adjusted.

In one or more embodiments, the polishing composition described herein may include at least one (e.g., two or three) barrier film removal rate enhancers. In some embodiments, at least one barrier film removal rate enhancer is an organic acid (e.g., carboxylic acid, amino acid, sulfonic acid, phosphoric acid, or phosphonic acid) or a salt thereof. In some embodiments, the barrier film removal rate enhancer may be an organic acid or a salt thereof selected from the group consisting of gluconic acid, lactic acid, citric acid, tartaric acid, apple acid, glycolic acid, malonic acid, formic acid, oxalic acid, acetic acid, propionic acid, peracetic acid, succinic acid, potassium acetate, potassium citrate, aminoacetic acid, phenoxyacetic acid, diglycine, diglycolic acid, glyceric acid, tricholoma, alanine, histidine, valine, isoleucine, Leucine, methionine, phenylalanine, cysteine, selenocysteine, glycine, proline, serine, threonine, asparagine, glutamine, aspartic acid, glutamine, arginine, histidine, lysine, tyrosine, tryptophan, benzoic acid, 1,2-ethanedisulfonic acid, 4-amino-3-hydroxy-1-naphthalenesulfonic acid, 8-hydroxyquinoline-5-sulfonic acid, aminomethanesulfonic acid, benzenesulfonic acid, hydroxyamine O-sulfonic acid, methyl Sulfonic acid, m-xylene-4-sulfonic acid, poly(4-styrenesulfonic acid), polyanethiosulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, ethylphosphonic acid, cyanoethylphosphonic acid, phenylphosphonic acid, vinylphosphonic acid, poly(vinylphosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid, nitrogen tris(methylphosphonic acid), diethylenetriamine penta(methylphosphonic acid), N,N,N',N'-ethylenediamine tetra(methylenephosphonic acid), n-hexylphosphonic acid, benzylphosphonic acid, phenylphosphonic acid, ethylenediaminetetraacetic acid, iminodiacetic acid, N-hydroxyethyl-ethylenediaminetriacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, triethylenetetraaminehexaacetic acid, diaminocyclohexanetetraacetic acid, nitrilotrimethylphosphonic acid, ethylenediaminetetra(methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, diethylenetriaminepenta(methylenephosphonic acid), salts thereof, and mixtures thereof. In one or more embodiments, the composition may include a second barrier film removal rate enhancer selected from nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, or a combination thereof. Without wishing to be bound by theory, it is unexpected that organic acids or salts thereof (such as those described above) can be used as effective barrier removal rate enhancers in the polishing compositions described herein to improve the removal rate of barrier films (e.g., Ta or TaN films) in semiconductor substrates.

In some embodiments, the amount of barrier film removal rate enhancer is at least about 0.02 wt % (e.g., at least about 0.05 wt %, at least about 0.1 wt %, at least about 0.2 wt %, at least about 0.4 wt %, at least about 0.5 wt %, at least about 0.6 wt %, at least about 0.8 wt %, at least about 1 wt %, at least about 1.5 wt %, or at least about 2 wt %) to at most about 4 wt % (e.g., at most about 3.5 wt %, at most about 3 wt %, at most about 2.5 wt %, at most about 2 wt %, at most about 1.5 wt %, or at most about 1 wt %) of the polishing composition described herein.

In one or more embodiments, the polishing composition described herein may include at least one (e.g., two or three) low-k removal rate inhibitor. In some embodiments, at least one low-k removal rate inhibitor is a non-ionic surfactant. In some embodiments, the non-ionic surfactant is the only low-k removal rate inhibitor in the polishing composition. In one or more embodiments, the non-ionic surfactant is selected from the group consisting of alcohol alkoxylates, alkylphenol alkoxylates, tristyrylphenol alkoxylates, sorbitan ester alkoxylates, polyalkoxylates, polyoxyalkylene block copolymers, alkoxylated diamines, and mixtures thereof. In one or more embodiments, the non-ionic surfactant is a polymer having a number average molecular weight of at least about 1,000 g/mol, or at least about 2,500 g/mol, or at least about 5,000 g/mol, or at least about 7,500 g/mol, or at least about 10,000 g/mol. In one or more embodiments, the non-ionic surfactant is a polymer having a number average molecular weight of at most about 1,000,000 g/mol, or at most about 750,000 g/mol, or at most about 500,000 g/mol, or at most about 250,000 g/mol, or at most about 100,000 g/mol. In one or more embodiments, the alkoxylate group of the alkoxylated non-ionic surfactant is an ethoxylate, a propoxylate, or a combination of an ethoxylate and a propoxylate group. Without wishing to be bound by theory, it is unexpected that non-ionic surfactants (such as those described above) can be used as low-k removal rate inhibitors in the polishing compositions described herein to reduce or minimize the removal rate of low-k films (e.g., carbon-doped silicon oxide films) in semiconductor substrates. In some embodiments, the polishing compositions described herein do not include alkylphenol alkoxylates.

In some embodiments, the amount of low-k removal rate suppressor is at least about 0.005 wt % (e.g., at least about 0.01 wt %, at least about 0.05 wt %, at least about 0.1 wt %, at least about 0.5 wt %, at least about 1 wt %, at least about 1.5 wt %, at least about 2 wt %, or at least about 3 wt %) to at most about 5 wt % (e.g., at most about 4.5 wt %, at most about 4 wt %, at most about 3.5 wt %, at most about 3 wt %, at most about 2.5 wt %, at most about 2 wt %, at most about 1.5 wt %, at most about 1 wt %, at most about 0.5 wt %, or at most about 0.1 wt %) of the polishing composition described herein.

In one or more embodiments, the polishing composition described herein may include at least one (e.g., two or three) azole-containing corrosion inhibitors. In some embodiments, at least one azole compound is selected from the group consisting of substituted or unsubstituted triazoles, substituted or unsubstituted tetrazoles, substituted or unsubstituted benzotriazoles, substituted or unsubstituted pyrazoles, substituted or unsubstituted imidazoles, substituted or unsubstituted benzimidazoles, substituted or unsubstituted thiadiazoles, substituted or unsubstituted thiabendazoles, substituted or unsubstituted adenines, substituted or unsubstituted xanthines, and substituted or unsubstituted guanines. In one or more embodiments, the azole compound can be selected from the group consisting of: 1,2,4-triazole, 1,2,3-triazole, tetrazole, benzotriazole, tolyltriazole, methylbenzotriazole (e.g., 1-methylbenzotriazole, 4-methylbenzotriazole or 5-methylbenzotriazole), ethylbenzotriazole (e.g., 1-ethylbenzotriazole), propylbenzotriazole (e.g., 1-propylbenzotriazole), butylbenzotriazole (e.g., 1-butylbenzotriazole or 5-butylbenzotriazole), pentylbenzotriazole (e.g., 1-pentylbenzotriazole), hexylbenzotriazole (e.g., 1-hexylbenzotriazole or 5-hexylbenzotriazole), dimethylbenzotriazole (e.g., 5,6-dimethylbenzotriazole), Chlorobenzotriazole (e.g., 5-chlorobenzotriazole), dichlorobenzotriazole (e.g., 5,6-dichlorobenzotriazole), chloromethylbenzotriazole (e.g., 1-(chloromethyl)-1-H-benzotriazole), chloroethylbenzotriazole, phenylbenzotriazole, benzylbenzotriazole, aminotriazole, aminobenzimidazole, aminotetrazolyl, pyrazole, imidazole, adenine, xanthine, guanine, benzimidazole, thiabendazole, 1-hydroxybenzotriazole, 2-methylbenzothiazole, 2-aminobenzimidazole, 2-amino-5-ethyl-1,3,4-thiadiazole, 3,5-diamine-1,2,4-triazole, 3-amino-5-methylpyrazole, 4-amino-4H-1,2,4-triazole, and mixtures thereof. Without wishing to be bound by theory, it is believed that azole compounds such as those described above can significantly reduce or minimize the removal rate of metals (e.g., copper) in semiconductor substrates.

In some embodiments, the amount of azole corrosion inhibitor is at least about 0.0001 wt % (e.g., at least about 0.0002 wt %, at least about 0.0005 wt %, at least about 0.001 wt %, at least about 0.002 wt %, at least about 0.005 wt %, at least about 0.01 wt %, at least about 0.02 wt %, at least about 0.05 wt %, at least about 0.1 wt %, at least about 0.2 wt %, or at least about 0.5 wt %) to at most about 1 wt % (e.g., at most about 0.8 wt %, at most about 0.6 wt %, at most about 0.5 wt %, at most about 0.4 wt %, at most about 0.2 wt %, at most about 0.1 wt %, at most about 0.05 wt %, at most about 0.02 wt %, at most about 0.01 wt %, or at most about 0.005 wt %) of the polishing composition described herein.

An optional oxidizing agent may be added when the concentrated slurry is diluted to form a POU slurry. The oxidizing agent may be selected from the group consisting of hydrogen peroxide, ammonium persulfate, silver nitrate (AgNO ₃ ), ferric nitrate or ferric chloride, acids or salts thereof; ozone water, potassium ferrocyanide, potassium dichromate, potassium iodate, potassium bromate, potassium periodate, periodic acid, vanadium trioxide, hypochlorous acid, sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, magnesium hypochlorite, ferric nitrate, potassium permanganate, other inorganic or organic peroxides, and mixtures thereof. In some embodiments, the oxidizing agent is hydrogen peroxide.

In some embodiments, the amount of oxidizing agent is at least about 0.05 wt % (e.g., at least about 0.1 wt %, at least about 0.2 wt %, at least about 0.4 wt %, at least about 0.5 wt %, at least about 1 wt %, at least about 1.5 wt %, at least about 2 wt %, at least about 2.5 wt %, at least about 3 wt %, at least about 3.5 wt %, at least about 4 wt %, or at least about 4.5 wt %) to at most about 5 wt % (e.g., at most about 4.5 wt %, at most about 4 wt %, at most about 3.5 wt %, at most about 3 wt %, at most about 2.5 wt %, at most about 2 wt %, at most about 1.5 wt %, at most about 1 wt %, at most about 0.5 wt %, or at most about 0.1 wt %) of the polishing composition described herein. In some embodiments, without wishing to be bound by theory, it is believed that the oxidizing agent can assist in the removal of the metal film by forming a metal complex with the chelating agent, allowing the metal to be removed during the CMP process. In some embodiments, without wishing to be bound by theory, it is believed that the metal complex formed between the metal film and the oxidizing agent can form a passivation layer that can protect the metal from corrosion. In some embodiments, the oxidizing agent can shorten the shelf life of the polishing composition. In such embodiments, the oxidizing agent can be added to the polishing composition at the time of use immediately prior to polishing.

In some embodiments, the polishing compositions described herein can include a solvent (eg, a primary solvent), such as water. In some embodiments, the amount of solvent (e.g., water) is at least about 20 wt % (e.g., at least about 25 wt %, at least about 30 wt %, at least about 35 wt %, at least about 40 wt %, at least about 45 wt %, at least about 50 wt %, at least about 55 wt %, at least about 60 wt %, at least about 65 wt %, at least about 70 wt %, at least about 75 wt %, at least about 80 wt %, at least about 85 wt %, at least about 90 wt %, at least about 92 wt %, at least about 94 wt %, at least about 95 wt %, or at least about 97 wt %) to up to about 99 wt % (e.g., up to about 98 wt %, up to about 96 wt %, up to about 94 wt %, up to about 92 wt %, up to about 90 wt %, up to about 85 wt %, up to about 80 wt %, up to about 75 wt %, up to about 70 wt %, or up to about 65 wt %) of the polishing composition described herein.

In one or more embodiments, an optional secondary solvent (e.g., an organic solvent) can be used in the polishing composition (e.g., POU or concentrated polishing composition) of the present disclosure, which can help dissolve the azole-containing corrosion inhibitor. In one or more embodiments, the secondary solvent can be one or more alcohols, alkanediols, or alkanediol ethers. In one or more embodiments, the secondary solvent comprises one or more solvents selected from the group consisting of ethanol, 1-propanol, 2-propanol, n-butanol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol propyl ether, and ethylene glycol.

In some embodiments, the amount of secondary solvent is at least about 0.0025 wt % (e.g., at least about 0.005 wt %, at least about 0.01 wt %, at least about 0.02 wt %, at least about 0.05 wt %, at least about 0.1 wt %, at least about 0.2 wt %, at least about 0.4 wt %, at least about 0.6 wt %, at least about 0.8 wt %, or at least about 1 wt %) to at most about 2 wt % (e.g., at most about 1.8 wt %, at most about 1.6 wt %, at most about 1.5 wt %, at most about 1.4 wt %, at most about 1.2 wt %, at most about 1 wt %, at most about 0.8 wt %, at most about 0.6 wt %, at most about 0.5 wt %, or at most about 0.1 wt %) of the polishing composition described herein.

In one or more embodiments, the polishing composition described herein may include at least one (e.g., two or three) anionic polymers. In one or more embodiments, the at least one anionic polymer may include one or more anionic groups, such as carboxylic acid groups, sulfate groups, and phosphoric acid groups. In one or more embodiments, the at least one anionic polymer is formed from one or more monomers selected from the group consisting of (meth)acrylic acid, maleic acid, acrylic acid, vinylphosphonic acid, vinylphosphonic acid, vinylsulfonic acid, allylsulfonic acid, styrenesulfonic acid, acrylamide, acrylamidopropylsulfonic acid, and sodium phosphite. In more specific embodiments, at least one anionic polymer can be selected from the group consisting of poly(4-phenylenesulfonic) acid (PSSA), polyacrylic acid (PAA), poly(vinylphosphonic acid) (PVPA), poly(2-acrylamido-2-methyl-1-propanesulfonic acid), poly(N-vinylacetamide) (PNVA), polyethyleneimine (PEI), anionic poly(methyl methacrylate) (PMMA), anionic polyacrylamide (PAM), polyaspartic acid (PASA), anionic poly(ethylene succinate) (PES), anionic polysuccinate (Succinate) ... The present invention relates to a copolymer of 2-acrylic acid, 2-methyl-2-((1-oxo-2-propenyl)amino)-1-propanesulfonic acid monosodium salt and sodium phosphite, a copolymer of 2-acrylic acid, 2-methyl-2-((1-oxo-2-propenyl)amino)-1-propanesulfonic acid monosodium salt and sodium hydrogen sulfite, and a 2-acrylamido-2-methyl-1-propanesulfonic acid-acrylic acid copolymer, a poly(4-styrenesulfonic acid-co-acrylic acid-co-vinylphosphonic acid) terpolymer, a phosphinocarboxylic acid, a hydrolyzed polymaleic anhydride, and a mixture thereof. Without wishing to be bound by theory, it is believed that the anionic polymer may help dissolve oxidized ruthenium species generated during the polishing process while also reducing the electrostatic forces between the abrasive particles and the ruthenium surface.

In one or more embodiments, the weight average molecular weight of at least one anionic polymer can range from at least about 250 g/mol (e.g., at least about 500 g/mol, at least about 1000 g/mol, at least about 2,000 g/mol, at least about 5,000 g/mol, at least about 50,000 g/mol, at least about 100,000 g/mol, at least about 200,000 g/mol, or at least about 250,000 g/mol) to at most about 500,000 g/mol (e.g., at most about 400,000 g/mol, at most about 300,000 g/mol, at most about 200,000 g/mol, at most about 100,000 g/mol, or at most about 50,000 g/mol, or at most about 10,000 g/mol). In some embodiments, the weight average molecular weight of at least one anionic polymer may be in the range of at least about 1000 g/mol to at most about 10,000 g/mol. In some embodiments, the weight average molecular weight of at least one anionic polymer may be in the range of at least about 2000 g/mol to at most about 6,000 g/mol. In some embodiments, at least one anionic polymer may have a weight average molecular weight of about 5,000 g/mol.

In some embodiments, the polishing compositions described herein include an anionic polymer, such as poly(vinylphosphonic acid), 2-acrylamido-2-methyl-1-propanesulfonic acid-acrylic acid copolymer, or poly(4-styrenesulfonic acid-co-acrylic acid-co-vinylphosphonic acid) terpolymer. In some embodiments, the polishing compositions described herein include two anionic polymers, such as (1) poly(4-styrenesulfonic) acid and poly(acrylic) acid or (2) 2-acrylamido-2-methyl-1-propanesulfonic acid-acrylic acid copolymer and poly(acrylic) acid.

In one or more embodiments, at least one anionic polymer is included in the cleaning composition in an amount of about 0.00001% to about 50% by weight. For example, at least one anionic polymer can be at least about 0.00001% (e.g., at least about 0.00005%, at least about 0.0001%, at least about 0.0005%, at least about 0.001%, at least about 0.005%, at least about 0.01%, at least about 0.05%, at least about 0.1%, at least about 0.5%, or at least about 1%) to at most about 50% (e.g., at most about 45%, at most about 40%, at most about 35%, at most about 30%, at most about 25%, at most about 20%, at most about 15%, at most about 10%, at most about 5%, or at most about 1%) by weight of the cleaning composition described herein.

In one or more embodiments, the polishing compositions described herein may be substantially free of one or more of certain ingredients, such as organic solvents, pH adjusters, zwitterionic compounds, quaternary ammonium compounds (e.g., salts such as tetraalkylammonium salts and hydroxides such as tetraalkylammonium hydroxide), alkali metals (e.g., alkali metal hydroxides), fluorine-containing compounds (e.g., fluorine compounds compounds or fluorinated compounds (such as fluorinated polymers/surfactants)), silicon-containing compounds such as silanes (for example, alkoxysilanes), nitrogen-containing compounds (for example, amino acids, amines or imines (for example, amidines, such as 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) and 1,5-diazabicyclo[4.3.0]non-5-ene (D BN)), amides or imides), salts (e.g., halides or metal salts), polymers (e.g., nonionic, cationic, anionic, or water-soluble polymers), inorganic acids (e.g., hydrochloric acid, sulfuric acid, phosphoric acid, or nitric acid), surfactants (e.g., cationic surfactants, anionic surfactants, non-polymeric surfactants, or non-ionic surfactants), plastics The present invention relates to a catalytic agent, an oxidizing agent (e.g., hydrogen peroxide and periodic acid), a corrosion inhibitor (e.g., an azole or non-azole corrosion inhibitor), an electrolyte (e.g., a polyelectrolyte), and/or certain abrasives (e.g., polymer abrasives, fumed silica, a bismuth oxide abrasive, a non-ionic abrasive, a surface modified abrasive, a negatively/positively charged abrasive, or a ceramic abrasive composite). Halides that can be excluded from the polishing composition include alkali metal halides (e.g., sodium halides or potassium halides) or ammonium halides (e.g., ammonium chloride), and can be fluorides, chlorides, bromides, or iodides. As used herein, a polishing composition is "substantially free" of an ingredient refers to an ingredient that is not intentionally added to the polishing composition. In some embodiments, the polishing compositions described herein may have up to about 1000 ppm (e.g., up to about 500 ppm, up to about 250 ppm, up to about 100 ppm, up to about 50 ppm, up to about 10 ppm, or up to about 1 ppm) of substantially free of one or more of the above ingredients of the polishing composition. In some embodiments, the polishing compositions described herein may be completely free of one or more of the above ingredients.

In one or more embodiments, the polishing compositions described herein can have a ratio of removal rate of silicon oxide (e.g., TEOS) to removal rate of Cu (i.e., removal rate selectivity) of at least about 0.5:1 (e.g., at least about 0.6:1, at least about 0.7:1, or at least about 0.8:1) to at most about 2:1 (e.g., at most about 1.8:1, at most about 1.6:1, at most about 1.4:1, at most about 1.2:1, or at most about 1:1). It should be noted that the term "silicon oxide" described herein is expressly intended to include both undoped and doped forms of silicon oxide. In some embodiments, the silicon oxide may be doped with at least one dopant selected from the group consisting of carbon, nitrogen, oxygen, hydrogen, or any other known silicon oxide dopant. Some examples of silicon oxide film types include tetraethyl orthosilicate (TEOS), SiOC, SiOCN, SiOCH, SiOH, and SiON. In one or more embodiments, the ratios and/or removal rates described above may be applicable when measuring removal rates of polishing blanket wafers or patterned wafers (e.g., wafers including conductive layers, barrier layers, and/or dielectric layers).

In one or more embodiments, when a wafer is polished using a polishing composition according to the present disclosure, the total defect count on a 12 inch (i.e., about 300 mm) diameter wafer (e.g., on a copper surface of the wafer) is at most 800 (e.g., at most 700, at most 600, at most 500, at most 400, at most 300, at most 250, at most 200, at most 150, at most 100, or at most 50). In one or more embodiments, the defects may be caused by scratches, organic residues, particle contamination (e.g., abrasives), and combinations thereof. Generally, defects can be counted by using a laser scattering detection system and then analyzed and classified by viewing images of the polished wafer taken using a scanning electron microscope (SEM). In one or more embodiments, the defects counted are those having a size of at least about 100 nanometers.

The present disclosure also encompasses a method of using any of the above-described polishing compositions (e.g., a concentrate or a POU slurry). In the case of a concentrate, the method may include the steps of diluting the concentrate to form a POU slurry (e.g., at least twice), and then contacting a surface at least partially comprising copper with the POU slurry. In some embodiments, an oxidizing agent may be added to the slurry before or after dilution. In the case of a POU slurry, the method includes the step of contacting a surface at least partially comprising copper with the polishing composition.

In one or more embodiments, the present disclosure features a polishing method that can include applying a polishing composition according to the present disclosure to a substrate (e.g., a wafer) having at least copper and silicon oxide on a substrate surface; and contacting a pad with the substrate surface and moving the pad relative to the substrate. Additionally, in some embodiments, after polishing a substrate using the polishing composition described herein, the polished substrate can be subjected to a rinse polishing process, wherein a composition including all components of the polishing composition (except an abrasive) is applied to the polished substrate in a polishing tool and a pad of the polishing tool is contacted with the substrate and moved relative to the substrate to produce a rinse polished substrate. In some embodiments, after a polishing process or a shower polishing process, the substrate may be removed from the polishing tool and subjected to post-CMP cleaning in a cleaning tool (eg, a brush scrubber or a spin shower dryer).

In some embodiments, methods using the polishing compositions described herein may further include producing semiconductor devices from substrates processed by the polishing compositions through one or more steps. For example, lithography, ion implantation, dry/wet etching, plasma ashing, deposition (e.g., PVD, CVD, ALD, ECD), wafer mounting, die cutting, packaging, and testing may be used to produce semiconductor devices from substrates processed by the polishing compositions described herein.

The following specific examples are to be construed as illustrative only and are not intended to limit the remainder of the present disclosure in any way. Without further detailed description, it is believed that one skilled in the art can utilize the present invention to its fullest extent based on the description herein. Examples

In these examples, polishing was performed on 200 mm wafers using an AMAT Mirra CMP polisher, Fujibo H804 pad, pressure below 1.7 psi, platen head speed of 120/114 rpm, and slurry flow rates of 150 mL/min and 225 mL/min.

The general compositions used in the Examples are shown below in Table 1. Specific details regarding the differences in the compositions tested are explained in further detail when discussing the individual Examples. Components Weight % of composition Inorganic alkaline pH adjusters 0.05-2.5 Organic Alkaline pH Regulator 0.05-2.5 (if used) Barrier film removal rate enhancer (acid) 0.02-2 Low-k Removal Rate Inhibitor 0.01-1 Azole-containing corrosion inhibitors 0.0001-0.1 Abrasive (Silicon Dioxide) 0.1-12 Anionic polymer (if present) 0.001-1 Oxidants 0.1-5 Solvent (deionized water) 80-99 pH 7-12 Example 1

Table 2 below shows the removal rates of Cu, TEOS, TaN and black diamond 1 (BD) when polishing using compositions 1 to 6. Compositions 1 to 6 contain the same ingredients at the same concentrations, except that the molar ratios of the organic base and the inorganic base identified in Table 2 are different. Composition 1 includes only the inorganic base, while composition 6 includes only the organic base and the two serve as controls. Each of compositions 2 to 5 includes a combination of organic bases and inorganic bases in several molar ratios, as shown in Table 2. BD blanket wafers are low-k dielectric materials (i.e., carbon-doped silicon oxide) coated on silicon wafers.

The results unexpectedly show that the combination of an organic base and an inorganic base is able to protect both Cu and TEOS more effectively (as indicated by its lower removal rates) than Composition 1 (which contains an inorganic base but no organic base). Importantly, the Cu and TEOS removal rates are reduced to similar degrees and generally produce a 1:1 removal rate ratio, which is preferred in some applications. Composition 6 (which contains an organic base but no inorganic base) is unable to maintain a 1:1 Cu to TEOS removal rate ratio due to a greatly reduced and industrially unacceptable copper removal rate. Table 2 Composition 1 vs. Inorganic Base Only Composition 2 MR=0.34 Composition 3 MR=0.74 Composition 4 MR=1.14 Composition 5 MR=1.56 Composition 6 vs. organic base only TEOS RR (Å/min) 111 98 90 79 69 52 Cu RR (Å/min) 110 98 90 75 64 37 BD RR (Å/min) 15 16 17 17 19 18 TaN RR (Å/min) 250 242 220 205 173 151 RR = Removal Rate ---MR = Molar Ratio of Organic Base to Inorganic Base Example 2

Table 3 below shows the removal rates of Cu and TEOS blanket wafers when polished using polishing compositions 1 and 3, which are detailed in Table 1 above, and newly present compositions 7 to 11. Composition 1, composition 3, and compositions 7 to 11 contain the same ingredients at the same concentrations, except for the differences identified below and in Table 3. Specifically, composition 1 includes only an inorganic base, while composition 3 and compositions 7 to 11 all include a combination of an organic base and an inorganic base at a molar ratio (organic:inorganic) of 0.74. The organic bases in composition 3 and compositions 7 to 11 are all different alkylammonium hydroxides. The organic base in compositions 10 and 11 is an alkylammonium hydroxide including a covalently bonded hydroxyl group, while compositions 3 and compositions 7 to 9 are alkylammonium hydroxides not including a covalently bonded hydroxyl group.

The results show that composition 3 and compositions 7 to 9 containing alkylammonium hydroxides without covalently bonded hydroxyl groups are able to protect both Cu and TEOS more effectively than composition 1 (which contains an inorganic base but no organic base) (as shown by their lower removal rates). In addition, compositions 3 and compositions 7 to 9 all maintain a 1:1 Cu to TEOS removal rate ratio, which is preferred in some applications. Unexpectedly, compositions 10 and 11 containing alkylammonium hydroxides including covalently bonded hydroxyl groups both produce excessively high TEOS removal rates and a 2:1 TEOS to copper removal rate ratio. Table 3 Composition 1 vs. Inorganic Base Only Composition 3 Organic base 1 Composition 7 Organic Base 2 Composition 8 Organic base 3 Composition 9 Organic base 4 Composition 10 Organic base 5 Composition 11 Organic base 6 TEOS RR (Å/min) 111 90 96 90 88 175 200 Cu RR (Å/min) 110 90 92 86 84 95 99 Example 3

Table 4 below shows the dissolution values (ppb) of the CuO and RuO ₂ particles incubated in Composition 1 and Composition 3. In the experiment, 0.005 grams of RuO ₂ particles or 0.01 grams of CuO particles were dynamically incubated with either of the compositions for one minute at room temperature. After this incubation, the mixture was centrifuged for 40 minutes and the amount of Cu or Ru dissolved in the supernatant after incubation was measured by ICP-MS.

The results unexpectedly show that composition 3 (which contains a mixture of inorganic and organic bases) significantly increases the dissolution of copper oxide (the main residue) and ruthenium oxide. This result suggests that composition 3 should remove abrasive particles more effectively than composition 1 and therefore leave a cleaner surface. Table 4 CuO (ppb) RuO ₂ (ppb) Composition 1 vs. Inorganic Base Only 4491 25 Composition 3 Organic base 1 10815 390 Example 4

Table 5 below shows the results of TOF-SIMS analysis of ruthenium residues on the copper portion of patterned coupons that were polished using compositions including anionic polymers (e.g., compositions 13 to 21) and compositions not including anionic polymers (i.e., control composition 12). The results in Table 5 are averages of multiple analyses and lower values indicate less ruthenium residues.

Compositions 13 to 20 each included a chemically distinct anionic polymer and composition 21 included the same anionic polymer as composition 17 along with a small amount of NH ₄ OH (e.g., 0.001 wt % to 0.05 wt %). The results show that the inclusion of the anionic polymer significantly reduced the amount of ruthenium residues detected on the copper portion of the polished coupons when compared to control composition 12. Furthermore, the addition of NH ₄ OH in composition 21 unexpectedly enhanced ruthenium residue removal. Table 5 Composition 12 control Composition 13 Composition 14 Composition 15 Composition 16 Composition 17 Composition 18 Composition 19 Composition 20 Composition 21 0.39 0.29 0.27 0.29 0.17 0.28 0.29 0.27 0.27 0.14

Although only a few exemplary embodiments have been described in detail above, those skilled in the art will readily appreciate that many modifications may be made to the exemplary embodiments without departing substantially from the present invention. Therefore, all such modifications are intended to be included within the scope of the present disclosure as defined in the following patent claims.

Claims (24)

A polishing composition comprising: an abrasive; at least two pH adjusters comprising at least one inorganic base and at least one organic base, wherein the molar ratio of the at least one organic base to the at least one inorganic base is about 0.05 to about 2; a barrier film removal rate enhancer; a low-k removal rate inhibitor; and an azole-containing corrosion inhibitor. The polishing composition of claim 1, wherein the abrasive is selected from the group consisting of: aluminum oxide, silicon dioxide, titanium dioxide, barium dioxide, zirconium oxide; a product formed from aluminum oxide, silicon dioxide, titanium dioxide, barium dioxide or zirconium oxide; a coating abrasive, a surface modification abrasive and a mixture thereof. The polishing composition of claim 1 or 2, wherein the amount of the abrasive is from about 0.1 wt % to about 50 wt % of the composition. The polishing composition of any one of claims 1 to 3, wherein the molar ratio of the at least one organic base to the at least one inorganic base is about 0.5 to about 2. The polishing composition of any one of claims 1 to 4, wherein the at least one inorganic base comprises a base selected from the group consisting of ammonium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, tantalum hydroxide, and any combination thereof. The polishing composition of any one of claims 1 to 5, wherein the at least one organic base comprises quaternary ammonium hydroxide, quaternary phosphonium hydroxide, or a guanidine compound. The polishing composition of claim 6, wherein the quaternary ammonium hydroxide or the quaternary phosphonium hydroxide is selected from the group consisting of tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, diethyldimethylammonium hydroxide, dimethyldipropylammonium hydroxide, benzyltrimethylammonium hydroxide, tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrapropylphosphonium hydroxide, tetrabutylphosphonium hydroxide, tetrapentylphosphonium hydroxide, triethyl-methyl-phosphonium hydroxide, tetrakis(hydroxymethyl)phosphonium hydroxide, tetraphenylphosphonium hydroxide, and any combination thereof. The polishing composition of claim 6 or 7, wherein the quaternary ammonium hydroxide or the quaternary phosphonium hydroxide does not include a covalently bonded hydroxyl group. The polishing composition of any one of claims 1 to 8, wherein the combined amount of the pH adjusters is from about 0.05 wt % to about 10 wt % of the composition. The polishing composition of any one of claims 1 to 9, wherein the barrier film removal rate enhancer is an organic acid or a salt thereof selected from the group consisting of gluconic acid, lactic acid, citric acid, tartaric acid, apple acid, glycolic acid, malonic acid, formic acid, oxalic acid, acetic acid, propionic acid, peracetic acid, succinic acid, potassium acetate, potassium citrate, aminoacetic acid, phenoxyacetic acid, diglycine, diglycolic acid, glyceric acid, tricholoma, alanine, histamine Acid, valine, isoleucine, leucine, methionine, phenylalanine, cysteine, selenocysteine, glycine, proline, serine, threonine, asparagine, glutamine, aspartic acid, glutamine, arginine, histidine, lysine, tyrosine, tryptophan, benzoic acid, 1,2-ethanedisulfonic acid, 4-amino-3-hydroxy-1-naphthalenesulfonic acid, 8-hydroxyquinoline-5-sulfonic acid, aminomethanesulfonic acid, benzenesulfonic acid, Hydroxylamine O-sulfonic acid, methanesulfonic acid, m-xylene-4-sulfonic acid, poly(4-styrenesulfonic acid), polyanetholsulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, ethylphosphonic acid, cyanoethylphosphonic acid, phenylphosphonic acid, vinylphosphonic acid, poly(vinylphosphonic acid), 1-hydroxyethane-1,1-diphosphonic acid, nitrogen tris(methylphosphonic acid), diethylenetriamine penta(methylphosphonic acid), N,N,N',N'-ethylenediamine tetra(methylenephosphonic acid), n-hexane phosphonic acid, benzylphosphonic acid, phenylphosphonic acid, ethylenediaminetetraacetic acid, iminodiacetic acid, N-hydroxyethyl-ethylenediaminetriacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, triethylenetetraaminehexaacetic acid, diaminocyclohexanetetraacetic acid, nitrilotrimethylphosphonic acid, ethylenediaminetetra(methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, diethylenetriaminepenta(methylenephosphonic acid), their salts, and mixtures thereof. The polishing composition of any one of claims 1 to 10, wherein the barrier film removal rate enhancer is in an amount of about 0.02 wt % to about 4 wt % of the composition. A polishing composition as claimed in any one of claims 1 to 11, wherein the low-k removal rate inhibitor is a non-ionic surfactant. The polishing composition of claim 12, wherein the non-ionic surfactant is selected from the group consisting of alcohol alkoxylates, alkylphenol alkoxylates, tristyrylphenol alkoxylates, sorbitan ester alkoxylates, polyalkoxylates, polyoxyalkylene block copolymers, alkoxylated diamines, and mixtures thereof. The polishing composition of any one of claims 1 to 13, wherein the low-k removal rate inhibitor is in an amount of about 0.005 wt % to about 5 wt % of the composition. The polishing composition of any one of claims 1 to 14, wherein the azole corrosion inhibitor is selected from the group consisting of triazole, tetrazole, benzotriazole, tolyltriazole, methylbenzotriazole, ethylbenzotriazole, propylbenzotriazole, butylbenzotriazole, pentylbenzotriazole, hexylbenzotriazole, dimethylbenzotriazole, chlorobenzotriazole, dichlorobenzotriazole, chloromethylbenzotriazole, chloroethylbenzotriazole, phenylbenzotriazole, benzylbenzotriazole, benzotriazole, 2-aminobenzimidazole, 2-amino-5-ethyl-1,3,4-thiadiazole, 3,5-diamine-1,2,4-triazole, 3-amino-5-methylpyrazole, 4-amino-4H-1,2,4-triazole, and mixtures thereof. The polishing composition of any one of claims 1 to 15, wherein the azole-containing corrosion inhibitor is in an amount of about 0.0001 wt % to about 1 wt % of the composition. The polishing composition of any one of claims 1 to 16, wherein the pH of the composition is about 7 to about 14. The polishing composition of any one of claims 1 to 17, wherein the at least one organic base comprises a first organic base and a second organic base different from the first organic base. The polishing composition of claim 18, wherein the first organic base is quaternary ammonium hydroxide or quaternary phosphonium hydroxide and the second organic base is selected from the group consisting of alkylamines, amino alcohols, guanidines, cyclic amines, and mixtures thereof. The polishing composition of any one of claims 1 to 19, further comprising at least one cationic polymer. A polishing composition as claimed in claim 20, wherein the at least one anionic polymer is formed from one or more monomers selected from the group consisting of: (meth)acrylic acid, cis-1,4-diene dicarboxylic acid, acrylic acid, acrylamide, apple acid, methacrylic acid, vinylphosphonic acid, vinylsulfonic acid, allylsulfonic acid, styrenesulfonic acid, acrylamide, acrylamidopropylsulfonic acid, phosphonic acid, phosphoric acid, vinylphosphonic acid, butadiene/cis-1,4-diene dicarboxylic acid, caprolactam, etherimide, 2-ethyl-2-oxazoline, N-isopropylacrylamide, sodium phosphite and their co-formed products, and their sodium salts, potassium salts and ammonium salts. A composition as claimed in claim 20, wherein the at least one anionic polymer comprises poly(4-styrenesulfonic) acid (PSSA), polyacrylic acid (PAA), poly(vinylphosphonic acid) (PVPA), poly(2-acrylamido-2-methyl-1-propanesulfonic acid), poly(N-vinylacetamide) (PNVA), anionic poly(methyl methacrylate) (PMMA), anionic polyacrylamide (PAM), 2-acrylamido-2-methyl-1-propanesulfonic acid-acrylic acid copolymer, poly(4-styrenesulfonic acid-co-acrylic acid-co-vinylphosphonic acid) terpolymer, phosphinocarboxylic acid, hydrolyzed polymaleic anhydride, or a mixture thereof. The composition of claim 20, wherein the at least one anionic polymer is present in an amount of about 0.00001 wt % to about 50 wt % of the cleaning composition. A method for polishing a substrate, comprising the steps of: Applying a polishing composition as in any one of claims 1 to 23 to a surface of a substrate, wherein the surface comprises copper and silicon oxide; and Contacting a pad with the surface of the substrate and moving the pad relative to the substrate.